4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.5.2]pentadecane | 213007-62-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.5.2]pentadecane
• 英文别名: 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane；4,11-Dimethyl-1,4,8,11-tetrazabicyclo[6.5.2]pentadecane
• CAS: 213007-62-6
• 化学式: C₁₃H₂₈N₄
• 分子量: 240.392
• InChiKey: IBPQXENBZARETM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.5.2]pentadecane 、 cobalt(II) chloride 以 乙腈 为溶剂， 生成 [CoCl2(4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane)]
  参考文献：
  名称：

  Synthesis, characterization, and X-ray crystal structures of cobalt(II) and cobalt(III) complexes of four topologically constrained tetraazamacrocycles

  摘要：

  The high spin Co2+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane (2), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (3), and racemic-4,5,7,7,11,12,14,14-octamethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (4) have been synthesized and characterized by X-ray crystallography. The Co(III) complexes of 1-3 were also prepared by the chemical oxidation of the Co(II) complexes. The X-ray crystal structures of Co(1)Cl-2, Co(3)Cl-2, and [Co(3)Cl-2]PF6 demonstrate that the ligands enforce a distorted octahedral geometry on Co(II) and Co(III) with two cis sites occupied by chloro ligands. In contrast, the Co(II) complex of 4 is five-coordinate with trigonal bipyramidal geometry. The methyl groups substituted on the carbon atoms of ligand 4 define a shallow cavity, allowing only one chloride ligand to bind to the chelated metal ion. This difference in coordination geometry causes Co(4)Cl+ to be much more difficult to oxidize (E-1/2 = 1.176 V vs. SHE) than the octahedral Co(II) complexes of 1-3 (E-1/2 from -0.157 to 0.173 V vs. SHE). The Co(III) complexes of 1-3 have three absorbances in their electronic spectra, while typical cis-Co(III)N4X2 complexes have only two. This additional splitting of energy states is attributed to the increased distortion from octahedral resulting from the short ethylene cross-bridge on the macrobicyclic ligands. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01080-0
• 作为产物：
  描述：

  2a,7a-dimethyl-cis-decahydro-2a,7a-diaza-4a,9a-diazoniacyclopenta[cd]phenalene diiodide 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 168.0h， 以98%的产率得到4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.5.2]pentadecane
  参考文献：
  名称：

  合成，结构研究，动力学稳定性和4,10-二甲基-1,4,7,10-四氮杂双环[6.5.2]十五烷的第一排过渡金属配合物的氧化催化†

  摘要：

  首次介绍了4,11-二甲基-1,4,8,11-四氮杂双环[6.5.2]十五烷的合成细节。已经合成并表征了其新颖的Mn 2 +，Fe 2 +，Mn 3+和Fe 3+配合物。获得了两种锰配合物的X射线晶体结构，以及另外五个Co 3+，Cu 2+和Zn 2+结构，这是该配体的配合物的第一个结构表征。每个复合物都具有跨桥大环环的cis -V构型，而保留了顺式使配合物与氧化剂和/或底物相互作用的不稳定结合位点。确定了铜（II）配合物在5 M HCl中和高温下的动力学稳定性，并将其与文献中的相关配合物进行了比较。使用固态磁矩测定和乙腈溶液电子光谱对锰和铁配合物的电子性质进行了评估，发现在所有情况下都具有高自旋金属配合物。二价铁和锰配合物在乙腈中的循环伏安法显示出可逆的氧化还原过程，表明这两种配合物均可能涉及涉及电子转移过程的催化反应性。Mn 2+和Fe 2+的筛选 用过氧化氢作为末端氧化剂进行氧化催化

  DOI：

  10.1039/c5dt00742a

文献信息

• Synthesis, structure, and stability in acid of copper(II) and zinc(II) complexes of cross-bridged tetraazamacrocycles
  作者：Timothy J Hubin、Nathaniel W Alcock、Martha D Morton、Daryle H Busch

  DOI：10.1016/s0020-1693(03)00036-7

  日期：2003.5

  New copper(II) and zinc(II) complexes of cross-bridged tetraazamacrocyclic ligands derived from 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,7,10-tetraazacyclotridecane([13]aneN4), and 1,4,7,10-tetraazacyclododecane (cyclen) have been synthesized. The X-ray crystal structures of the two cyclen-derived complexes have been determined and show both metal ions to be in distorted octahedral environments with the ligand in a cis-folded conformation. The bridged-ligand complexes are remarkably stable kinetically under harsh acidic conditions, as seen from their dissociation reactions. The electrochemical and spectroscopic properties of the Cu2+ complexes have also been investigated. (C) 2003 Elsevier Science B.V. All rights reserved.
• Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane
  作者：Dallas L. Matz、Donald G. Jones、Kimberly D. Roewe、Michael-Joseph Gorbet、Zhan Zhang、Zhuqi Chen、Timothy J. Prior、Stephen J. Archibald、Guochuan Yin、Timothy J. Hubin

  DOI：10.1039/c5dt00742a

  日期：——

  and/or substrates. The copper(II) complex kinetic stability in 5 M HCl and at elevated temperatures was determined and compared to related complexes in the literature. The electronic properties of the manganese and iron complexes were evaluated using solid state magnetic moment determination and acetonitrile solution electronic spectroscopy, revealing high spin metal complexes in all cases. Cyclic voltammetry

  首次介绍了4,11-二甲基-1,4,8,11-四氮杂双环[6.5.2]十五烷的合成细节。已经合成并表征了其新颖的Mn 2 +，Fe 2 +，Mn 3+和Fe 3+配合物。获得了两种锰配合物的X射线晶体结构，以及另外五个Co 3+，Cu 2+和Zn 2+结构，这是该配体的配合物的第一个结构表征。每个复合物都具有跨桥大环环的cis -V构型，而保留了顺式使配合物与氧化剂和/或底物相互作用的不稳定结合位点。确定了铜（II）配合物在5 M HCl中和高温下的动力学稳定性，并将其与文献中的相关配合物进行了比较。使用固态磁矩测定和乙腈溶液电子光谱对锰和铁配合物的电子性质进行了评估，发现在所有情况下都具有高自旋金属配合物。二价铁和锰配合物在乙腈中的循环伏安法显示出可逆的氧化还原过程，表明这两种配合物均可能涉及涉及电子转移过程的催化反应性。Mn 2+和Fe 2+的筛选 用过氧化氢作为末端氧化剂进行氧化催化
• Synthesis, characterization, and X-ray crystal structures of cobalt(II) and cobalt(III) complexes of four topologically constrained tetraazamacrocycles
  作者：Timothy J Hubin、Nathaniel W Alcock、Howard J Clase、Lawrence L Seib、Daryle H Busch

  DOI：10.1016/s0020-1693(02)01080-0

  日期：2002.9

  The high spin Co2+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane (2), 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (3), and racemic-4,5,7,7,11,12,14,14-octamethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (4) have been synthesized and characterized by X-ray crystallography. The Co(III) complexes of 1-3 were also prepared by the chemical oxidation of the Co(II) complexes. The X-ray crystal structures of Co(1)Cl-2, Co(3)Cl-2, and [Co(3)Cl-2]PF6 demonstrate that the ligands enforce a distorted octahedral geometry on Co(II) and Co(III) with two cis sites occupied by chloro ligands. In contrast, the Co(II) complex of 4 is five-coordinate with trigonal bipyramidal geometry. The methyl groups substituted on the carbon atoms of ligand 4 define a shallow cavity, allowing only one chloride ligand to bind to the chelated metal ion. This difference in coordination geometry causes Co(4)Cl+ to be much more difficult to oxidize (E-1/2 = 1.176 V vs. SHE) than the octahedral Co(II) complexes of 1-3 (E-1/2 from -0.157 to 0.173 V vs. SHE). The Co(III) complexes of 1-3 have three absorbances in their electronic spectra, while typical cis-Co(III)N4X2 complexes have only two. This additional splitting of energy states is attributed to the increased distortion from octahedral resulting from the short ethylene cross-bridge on the macrobicyclic ligands. (C) 2002 Elsevier Science B.V. All rights reserved.